This invention pertains to thermally-stable, colored, photopolymerizable compounds containing a vinyl group which are capable of being copolymerized with reactive vinyl monomers to produce colored compositions such as polyacrylates, polymethacrylates, polystyrene, etc. The compounds exhibit good thermal stability, fastness (stability) to UV-light, good solubility in the reactive monomers and good color strength.
It is known (J.S.D.C., Apr. 1977, pp 114-125) to produce colored polymeric materials by combining a reactive polymer such terepolymers having epoxy groups or polyacryloyl chloride with anthraquinone dyes containing nucleophilic reactive groups such as amino or hydroxy groups; to graft acryloylaminoanthraquinone dyes to the backbone of vinyl or divinyl polymers; and to polymerize anthraquinone dyes containing certain olefinic groups to produce polymeric dyes/pigments. U.S. Pat. No. 4,115,056 describes the preparation of blue, substituted 1,4-diaminoanthraquinone dyes containing one acryloyloxy group and and the use of the dyes in coloring various fibers, especially polyamide fibers. U.S. Pat. No. 4,943,617 discloses liquid crystalline copolymers containing certain blue, substituted 1,5-diamino-4,8-dihydroxyanthraquinone dyes containing an olefinic group copolymerized therein to provide liquid crystal copolymers having high dichromism. U.S. Pat. No. 5,055,602 describes the preparation of certain substituted 1,4-diaminoanthraquinone dyes containing polymerizable acryloyl and methacryloyl groups and their use in coloring polyacrylate contact lens materials by copolymerizing.
U.S. Pat. No. 5,362,812 discloses the conversion of a variety of dye classes, including anthraquinones, into polymeric dyes by (a) polymerizing 2-alkenylazlactones and reacting the polymer with dyes containing nucleophilic groups and by (b) reacting a nucleophilic dye with an alkenylazlactone and then polymerizing the free radically polymerizable dyes thus produced. The polymeric dyes are reported to be useful for photoresist systems and for colorproofing. U.S. Pat. No. 5,367,039 discloses a process for preparing colored vinyl polymers suitable for inks, paints, toners and the like by emulsion polymerization of a vinyl monomer with reactive anthraquinone dyes prepared by functionalizing certain anthraquinone dyes with methacryloyl groups.
The preparation of a variety of dyes, including some anthraquinones, which contain photopolymerizable groups and their use for color filters suitable for use in liquid crystal television sets, color copying machines, photosensitive resist resin compositions, and the like are described in U.S. Pat. No. 5,578,419.
One embodiment of the present invention concerns thermally-stable, photopolymerizable dye or colorant compounds having having Formula I: 
wherein
A is a mono-, di-, tri- or tetravalent chromophore;
R1 is selected from hydrogen, C1-C6 alkyl, substituted C1-C6 alkyl, C3-C8 cycloalkyl, aryl and xe2x80x94R2xe2x80x94OQ;
R2 is selected from C2-C8 alkylene, arylene, C3-C8 cycloalkylene, arylene-C1-C6 alkylene, arylene-oxy-C1-C6 alkylene, arylenethio-C1-C6 alkylene, 1,4-cyclohexylenedimethylene and xe2x80x94(xe2x80x94CH2CH2O)mxe2x80x94CH2CH2xe2x80x94;
m is 1-3;
n is 1-4;
Q is an ethylenically-unsaturated, photopolymerizable group selected from the following organic radicals: 
wherein
R3 is selected from hydrogen or C1-C6 alkyl;
R4 is selected from hydrogen, C1-C6 alkyl; phenyl; phenyl substituted with one or more groups selected from C1-C6 alkyl, C1-C6 alkoxy, xe2x80x94N(C1-C6 alkyl)2, nitro, cyano, C2-C6 alkoxycarbonyl, C2-C6 alkanoyloxy and halogen; 1- and 2-naphthyl; 1- and 2-naphthyl substituted with C1-C6 alkyl and C1-C6 alkoxy; 2- and 3-thienyl; 2- and 3-thienyl substituted with C1-C6 alkyl or halogen; 2- and 3-furyl; 2- and 3-furyl substituted with C1-C6 alkyl;
R5 and R6 are independently selected from hydrogen, C1-C6 alkyl, substituted C1-C6 alkyl, aryl or may be combined to represent a xe2x80x94(xe2x80x94CH2xe2x80x94)xe2x80x943-5 radical;
R7 is hydrogen or a group selected from C1-C6 alkyl, substituted C1-C6 alkyl, C3-C8 alkenyl, C3-C8 cycloalkyl and aryl;
R9 is selected from hydrogen, C1-C6 alkyl and aryl.
A second embodiment of the present invention pertains to a coating composition comprising (i) one or more polymerizable vinyl compounds, (ii) one or more of the thermally-stable, photopolymerizable dye or colorant compounds of Formula I, and (iii) a photoinitiator. A third embodiment of the present invention pertains to a polymeric composition, typically a coating, comprising a polymer of one or more acrylic acid esters, one or more methacrylic acid esters and/or other polymerizable vinyl compounds, having copolymerized therein one or more of the dye compounds of Formula I.
In formula I, A represents a mono-, di-, tri- or tetravalent residue of a chromophore, i.e., a colored compound. Examples of the chromophoric residues which A may represent include anthraquinone, anthrapyridone (3H-dibenz-[f, ij]-isoquinoline-2,7-dione), anthrapyrimidine (7H-benzo-[e]-perimidine-7-one), anthrapyridine (7H-dibenz-[f, ij]-isoquinoline-7-one), anthrapyrazole, anthraisothiazole, 14H-naptho[2,3-a]-phenothiazine-8,13-dione (phthaloylphenothiazine), phthalocyanine, metal phthalocyanine, methine, bis-methine, perinone, coumarin, quinophthalone, 3-aryl-2,5-dioxypyrroline, and 3-aryl-5-dicyanomethylene-2-oxypyrroline.
The terms xe2x80x9cC1-C6-alkylxe2x80x9d and xe2x80x9cC1-C8-alkylxe2x80x9d are used herein to denote a straight or branched chain saturated aliphatic hydrocarbon radical containing one to six or one to eight carbon atoms. The term xe2x80x9csubstituted C1-C6-alkylxe2x80x9d is used to denote a C1-C6-alkyl group substituted with one or more groups, preferably one to three groups, selected from the group consisting of hydroxy, halogen, cyano, aryl, aryloxy, arylthio, C1-C6 alkylthio, C3-C8-cycloalkyl, C2-C6-alkanoyloxy and xe2x80x94(xe2x80x94OR9xe2x80x94)pxe2x80x94R10 wherein R9 is selected from the group consisting of C1xe2x80x94C6 alkylene, C1-C6-alkylene-arylene, cyclohexylene, arylene, C1-C6-alkylene-cyclohexylene and C1-C6-alkylene-cyclohexylene-C1-C6-alkylene; R10 is selected from the group consisting of hydrogen, hydroxy, carboxy, C2-C6-alkanoyloxy, C2-C6-alkoxycarbonyl, aryl and C3-C8-cycloalkyl; and p is 1, 2, or 3.
The terms xe2x80x9cC1-C6-alkylenexe2x80x9d, xe2x80x9cC2-C6-alkylenexe2x80x9d and xe2x80x9cC2-C8 alkylenexe2x80x9d are used to denote straight or branched chain divalent aliphatic hydrocarbon radicals containing one to six, two to six, and two to eight carbons, respectively, which optionally may be substituted with one to three groups selected from C1-C6-alkoxy, C2-C6-alkoxycarbonyl, C2-C6-alkanoyloxy, hydroxy, aryl and halogen. The term xe2x80x9cC3-C8-alkenylxe2x80x9d is used to denote an aliphatic hydrocarbon radical containing at least one double bond. The term xe2x80x9cC3-C8-alkynylxe2x80x9d is used to denote an aliphatic hydrocarbon radical containing at least one triple bond and three to eight carbon atoms. The term xe2x80x9cC3-C8-cycloalkylxe2x80x9d is used to denote a saturated cyclic hydrocarbon radical having three to eight carbon optionally substituted with one to three C1-C6-alkyl group(s). The term xe2x80x9cC3-C8-cycloalkylenexe2x80x9d is used to denote a cyclic divalent hydrocarbon radical which contains three to eight carbon atoms, preferably five or six carbons.
The term xe2x80x9carylxe2x80x9d as used herein denotes phenyl and phenyl substituted with one to three substituents selected from C1-C6-alkyl, substituted C1-C6-alkyl, C1-C6-alkoxy, halogen, carboxy, cyano, C2-C6-alkanoyloxy, C1-C6-alkylthio, C1-C6-alkylsulfonyl, trifluoromethyl, hydroxy, optionally substituted sulfamoyl, C2-C6-alkoxycarbonyl, C2-C6-alkanoylamino and xe2x80x94Oxe2x80x94R11, Sxe2x80x94R11, xe2x80x94SO2xe2x80x94R11, xe2x80x94NHSO2R11 and xe2x80x94NHCO2R11, wherein R11 is phenyl or phenyl substituted with one to three groups selected from C1-C6-alkyl, C1-C6-alkoxy and halogen. The term xe2x80x9carylenexe2x80x9d as used herein denotes includes 1,2-, 1,3- and 1,4-phenylene and such divalent radicals substituted with one to three groups selected from C1-C6-alkyl, C1-C6-alkoxy and halogen. The term xe2x80x9caroylxe2x80x9d denotes a moiety having the formula xe2x80x94COxe2x80x94R11 wherein R11 is defined above.
The term xe2x80x9chalogenxe2x80x9d is used to include fluorine, chlorine, bromine, and iodine. The term xe2x80x9coptionally substituted sulfamoylxe2x80x9d is used to describe the group having the structure xe2x80x94SO2N(R12)R13, wherein R12, and R13 are independently selected from hydrogen, C1-C6-alkyl, substituted C1-C6-alkyl, C3-C8-alkenyl, C3-C8-cycloalkyl, aryl and heteroaryl. The terms xe2x80x9cC1-C6-alkoxyxe2x80x9d, xe2x80x9cC2-C6-alkoxycarbonylxe2x80x9d, xe2x80x9cC2-C6-alkanoylxe2x80x9d, xe2x80x9cC2-C6-alkanoyloxyxe2x80x9d and xe2x80x9cC2-C6-alkanoylaminoxe2x80x9d are used to denote radicals corresponding to the structures xe2x80x94OR14, xe2x80x94COR14, xe2x80x94CO2R14, xe2x80x94OCOR14 and NHCOR14, respectively, wherein R14 is C1-C6-alkyl or substituted C1-C6-alkyl.
The term xe2x80x9cheteroarylxe2x80x9d as used herein denotes a 5- or 6-membered aromatic ring containing one to three hetero atom selected from oxygen, sulfur and nitrogen. Examples of such heteroaryl groups are thienyl, furyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, triazolyl, thiadiazolyl, oxadiazolyl, tetrazolyl, pyridyl, pyrimidyl, benzoxazolyl, benothiazolyl, benzimidazolyl, indolyl and the like and these optionally substituted with one to three groups selected from C1-C6-alkyl, C1-C6-alkoxy, substituted C1-C6-alkyl, halogen, C1-C6-alkylthio, aryl, arylthio, aryloxy, C2-C6-alkoxycarbonyl and C2-C6-alkanoylamino.
The preferred anthraquinone dyes or colorants of the invention which correspond to Formula I have the following structures: 
wherein R15 is hydrogen or R15 represents 1-4 groups selected from amino; C1-C8-alkylamino; C1-C8-alkylamino substituted with one or more groups selected from hydroxy, cyano, halogen, aryl, heteroaryl, C3-C8-cycloalkyl, furyl, C1-C6-alkoxy, C1-C6-alkylthio, arylthio, aryloxy and xe2x80x94OCH2CH2O(OCH2CH2)1-3ORxe2x80x2, wherein Rxe2x80x2 is selected from hydrogen, C1-C6-alkyl and C2-C6-alkanoyloxy; C3-C8-cycloalkylamino; C3-C8-alkenylamino; C3-C8-alkynylamino; arylamino; furfurylamino; C1-C6-alkoxy; xe2x80x94OCH2CH2(OCH2CH2)1-3ORxe2x80x2, wherein Rxe2x80x2 is as previously defined; halogen; hydroxy; C1-C6-alkylthio; arylthio; aryl; aryloxy; arylsulfonyl; C2-C6-alkanoyl; aroyl; C2-C6-alkanoyloxy; C2-C6-alkoxycarbonyl; heteroaryl; heteroarylthio; cyano; nitro; trifluoromethyl; thiocyano; xe2x80x94SO2C1-C6-alkyl; xe2x80x94SO2NH2; xe2x80x94SO2NHC1-C6-alkyl; xe2x80x94SO2N(C1-C6 alkyl)2; xe2x80x94SO2N(C1-C6 alkyl)aryl; xe2x80x94SO2NH-aryl; xe2x80x94CONH2; xe2x80x94CONHC1-C6-alkyl; xe2x80x94CON(C1-C6-alkyl)2; xe2x80x94CONH-aryl; xe2x80x94CON(C1-C6alkyl) aryl; C1-C6 alkyl; tetrahydrofurfurylamino; xe2x80x94CH2-cyclohexane-1,4-diyl-CH2ORxe2x80x2, wherein Rxe2x80x2 is as previously defined; or 
R16 is hydrogen or 1-2 groups selected from C1-C6-alkyl, C1-C6-alkoxy and halogen;
R17 is selected from amino; C1-C8-alkylamino, substituted C1-C8-alkylamino is defined above, C3-C8-cycloalkylamino, C3-C8-alkenylamino, C3-C8-alkynylamino and arylamino;
R18 is selected from halogen, amino, C1-C8 alkylamino, substituted C1-C8-alkylamino, C3-C8-cycloalkylamino, C3-C8-alkenylamino, C3-C8-alkynylamino, arylamino, hydroxy, arylthio, heteroarylthio, C2-C6-alkanoylamino, aroylamino, C1-C6-alkylsulfonylamino, and arylsulfonylamino;
X is a covalent bond or a linking group selected from xe2x80x94Oxe2x80x94, xe2x80x94Sxe2x80x94, xe2x80x94SO2xe2x80x94, xe2x80x94NHCOxe2x80x94, xe2x80x94NHSO2xe2x80x94, xe2x80x94NHCONHxe2x80x94, xe2x80x94OC2-C6 alkylene-, xe2x80x94OC2-C6-alkylene-Oxe2x80x94, xe2x80x94Sxe2x80x94C2-C6-alkylene-Oxe2x80x94 and, xe2x80x94O(CH2CH2O)1-3xe2x80x94; and
R1, R2, Q and n are as defined above for Formula I.
Preferred anthrapyridone (3H-dibenz[f, ij]-isoquinoline-2,7-diones) and anthrapyridine (7H-dibenz-[f, ij]-isoquinoline-7-ones) colorant compounds provided by the present invention have the following general formulas: 
wherein:
R19 is selected from hydrogen, cyano, C1-C6-alkoxy, C1-C6-alkylthio, aryl, arylamino, aryloxy, arylthio, heteroaryl, heteroarylthio, halogen, C2-C6-alkoxycarbonyl, aroyl, C1-C6-alkylsulfonyl, arylsulfonyl and C1-C6-alkylamino;
R20 is selected from hydrogen, C1-C8-alkyl, substituted C1-C8-alkyl as defined above, aryl and C3-C8-cyloalkyl;
R2, is selected from hydrogen, C1-C6-alkyl, aryl and xe2x80x94N(R22)R23, wherein R22 and R23 are independently selected from hydrogen, C3-C8-cycloalkyl, C1-C6-alkyl and C1-C6-alkyl substituted with C1-C6-alkoxy, hydroxy, halogen, C2-C6-alkanoyloxy, aryl and C3-C8-cycloalkyl; wherein R22 and R23 also may be combined to produce divalent radicals such as (xe2x80x94CH2xe2x80x94)4-6 and xe2x80x94CH2CH2xe2x80x94Lxe2x80x94CH2CH2xe2x80x94, wherein L is a divalent linking group selected from xe2x80x94Oxe2x80x94, xe2x80x94Sxe2x80x94, xe2x80x94SO2xe2x80x94 and xe2x80x94N(R24), wherein R24 is selected from hydrogen, C1-C6-alkyl, aryl, aroyl, C2-C6-akanoyl, C1-C6-alkylsulfonyl and arylsulfonyl; and
R1, R2, R15, R16, xe2x80x94Xxe2x80x94, Q and n are defined above.
The thermally stable photopolymerizable colorants of Formula I may be prepared by reacting sulfonyl chlorides of Formula II with amines of Formula III, 
wherein Rxe2x80x2 is selected from hydrogen, C1-C6 alkyl, substituted C1-C6 alkyl, C3-C8-cycloalkyl, aryl and xe2x80x94R2OH, in the presence of base or enough excess amine reactant III to serve as acid acceptor. Typical useful bases are alkali metal carbonates, alkali metal bicarbonates, trialkylamines, etc. The reactions may be carried out in excess amine reactant HN(Rxe2x80x2)R2OH or in solvents such as ketones, pyridine, N,N-dimethylformamide (DMF), N-methyl-2-pyrrolidinone (NP), N,N-dimethylacetamide (DMAC), sulfolane, etc. The colored intermediate hydroxy compounds IV thus produced are then acylated with one or more ethylenically-unsaturated, acylating agent to yield the colorants of Formula I. Examples of the ethylenically-unsaturated acylating agents include compounds having the formulas: 
Examples of intermediate sulfonyl chlorides II useful in the practice of the invention are described in U.S. Pat. Nos. 4,403,092; 5,372,864; 5,453,482; 6,022,944 and Published PCT Application WO 98/23690. Additional sulfonyl chlorides of formula II are known and/or can be prepared according to published procedures.